Cationic aminodianthraquinones, use, dyeing compositions containing them and methods of dyeing

ABSTRACT

The invention relates to cationic aminodianthraquinones containing at least one cationic group Z, Z being chosen from quaternized aliphatic chains, aliphatic chains containing at least one quaternized saturated ring and aliphatic chains containing at least one quaternized unsaturated ring, their use as direct dye in compositions for dyeing keratinous materials, in particular human keratinous fibers such as hair, the dyeing compositions containing them, as well as the dyeing methods using them.

The present invention relates to cationic aminodianthraquinonescontaining at least one cationic group Z, with Z being chosen fromquaternized aliphatic chains, aliphatic chains containing at least onequaternized saturated ring, and aliphatic chains containing at least onequaternized unsaturated ring, their use as direct dyes in applicationsfor dyeing keratinous materials, such as human keratinous fibers, forexample hair, the dyeing compositions containing them, as well as thedyeing methods using them.

It is known to dye keratinous fibers, and in particular hair, withdyeing compositions containing direct dyes. Direct dyes are dyemolecules having affinity for keratinous fibers. The dyeing method whichuses them is a so-called direct dyeing method which comprises allowingthe direct dyes to act on the fibers, and subsequently rinsing thefibers.

The colors resulting therefrom are temporary or semipermanent colors,because the nature of the interactions which links the direct dyes tothe keratinous fiber, and their desorption from the surface and/or thecore of the fiber are responsible for their weak dyeing power, and theirpoor resistance to washings and perspiration.

Cationic aminoanthraquinones have already been described among the knowndirect dyes. Such aminoanthraquinones are described in, for example,French Patent Nos. 1,422,016 (and its addition 87,902), 1,391,675,1,401,163, 1,379,649, 1,430,089, 1,584,965, 2,050,397, 2,548,895, U.S.Pat. Nos. 5,169,403, 5,314,505, 5,486,629, 5,520,707, and EuropeanPatent Nos. 818,193 and 852,136, and contain only one anthraquinonenucleus.

However, in hair dyeing, direct dyes are being continually sought whichexhibit increasingly better characteristics.

It is thus after major research studies carried out on this subject thatthe inventors have discovered a new class of cationicaminoanthraquinones, the cationic aminodianthraquinones containing atleast one cationic group Z, with Z being chosen from quaternizedaliphatic chains, aliphatic chains containing at least one quaternizedsaturated ring, and aliphatic chains containing at least one quaternizedunsaturated ring.

This new family of dyes can exhibit the very advantageous characteristicfeature of greater solubility in the dyeing media. These new dyes canalso generate colors, by direct dyeing, having an intensity and aresistance to various attacks to which the hair may be subjected: light,adverse weather conditions, shampoos, and perspiration, which issubstantially improved compared with that of the colors produced withknown prior art cationic aminoanthraquinones.

This discovery forms the basis of the present invention.

A subject of the present invention is thus the aminodianthraquinones offormula (I)

in which formula,

B is a linking chosen from a linear or branched alkyl chain preferablycontaining 1 to 14 carbon atoms, which may be interrupted by one or moregroups Z, defined below, one or more heteroatoms such as oxygen, sulphuror nitrogen atoms, or a mixture of one or more groups Z and one or moreheteroatoms; and which may be unsubstituted or substituted with one ormore hydroxyl or C₁-C₆ alkoxy radicals, and which may carry one or moreketone functions;

R₁, R₂, R₃, R₄, R′₁, R′₂, R′₃ and R′₄, which may be identical ordifferent, are chosen from one of the two valencies of a linking arm B;a hydrogen atom; a halogen atom; a group Z, defined below; a(C₁-C₆)alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a cyano radical; a nitro radical; acarboxyl radical; a carbamyl radical; a sulpho radical; a substituted orunsubstituted amino radical, having the same meanings as NHR₅ or NHR′₅defined below, and which may be identical or different; a group OR₆ orSR₆ or OR′₆ or SR′₆ defined below; R₅ and R′₅, which may be identical ordifferent, are chosen from one of the two valencies of a linking arm B;a hydrogen atom; a group Z, defined below; a C₁-C₆ alkyl radical; amonohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl) radical; a(C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; a benzyl radical; acyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a thiocarbamyl(C₁-C₆alkyl) radical; a trifluoro(C₁-C₆ alkyl) radical; a sulpho(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆alkyl) radical; an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarbonyl(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl)radical, wherein the alkyl is unsubstituted or substituted with at leastone hydroxyl radical; an amino(C₁-C₆ alkyl) radical, wherein the alkylis unsubstituted or substituted with at least one hydroxyl radical, andwherein the amine is substituted with at one or two radicals, identicalor different, chosen from the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl),polyhydroxy(C₂-C₆ alkyl), (C₁-C₆)alkylcarbonyl, carbamyl,N-(C₁-C₆)alkylcarbamyl or N, N-di(C₁-C₆)alkylcarbamyl,(C₁-C₆)alkylsulphonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, and thiocarbamyl radicals, or from the group Z,defined below, or which may form, together with the nitrogen atom towhich they are attached, a 5- or 6-membered ring containing carbon orcontaining at least one heteroatom;

R₆ and R′₆, which may be identical or different, are chosen from one ofthe two valencies of a linking arm B; a hydrogen atom; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a group Z, defined below; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical;

an aryl radical; a benzyl radical; a carboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical;a carbamyl(C₁-C₆ alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl)radical; an N,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; atrifluoro(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆ alkyl) radical;an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarbonyl(C₁-C₆alkyl) radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical; anamino(C₁-C₆ alkyl) radical, wherein the alkyl is unsubstituted orsubstituted with at least one hydroxyl radical, and wherein the amine issubstituted with one or two radicals, identical or different, chosenfrom the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl), polyhydroxy(C₂-C₆alkyl), (C₁-C₆)alkylcarbonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, carbamyl, N-(C₁-C₆)alkylcarbamyl,N,N-di(C₁-C₆)alkylcarbamyl, thiocarbamyl, and (C₁-C₆)alkylsulphonylradicals, the groups Z, defined below, or which may form, together withthe nitrogen atom to which they are attached, a 5- or 6-membered ringcontaining carbon or containing at least one heteroatom;

Z is chosen from the unsaturated cationic groups of the formulae (11)and (111), and the saturated cationic groups of the formula (IV):

 in which:

D is a linking arm chosen from linear and branched alkyl chains,preferably containing from 1 to 14 carbon atoms, which may beinterrupted by one or more heteroatoms such as oxygen, sulphur ornitrogen, and which may be substituted with at least one radical chosenfrom hydroxyl and C₁-C₆ alkoxy, and which may carry at least one ketonefunction;

the members E, G, J, L and M, which are identical or different, arechosen from carbon, oxygen, sulphur and nitrogen atoms;

n is an integer ranging from 0 to 4;

m is an integer ranging from 0 to 5;

the radicals R, which are identical or different, are chosen from one ofthe two valencies of a linking arm B, a second group Z′, which has thesame definition as the group Z, and which is identical or different fromthe first group Z; a halogen atom; a hydroxyl radical; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a nitro radical; a cyano radical; a cyano(C₁-C₆ alkyl) radical;a C₁-C₆ alkoxy radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; anamido radical; an aldehydo radical; a carboxyl radical; a C₁-C₆alkylcarbonyl radical; a thio radical; a thio(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylthio radical; an amino radical; an amino radical protectedwith a (C₁-C₆)alkylcarbonyl, carbamyl or (C₁-C₆)alkylsulphonyl radical;a group NHR″ or NR″R′″, wherein R″ and R′″, which are identical ordifferent, are chosen from a C₁-C₆ alkyl radical, a monohydroxy(C₁-C₆alkyl) radical and a polyhydroxy(C₂-C₆ alkyl) radical;

R₇ is chosen from one of the two valencies of a linking arm B; a C₁-C₆alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆alkyl) radical; a cyano(C₁-C₆ alkyl) radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl)radical; a carbamyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆alkyl) radical; a benzyl radical, and a second group Z′, which has thesame definition as the group Z, which is identical or different from thegroup Z;

R₈, R₉ and R₁₀, which are identical or different, are chosen from one ofthe two valencies of a linking arm B; a C₁-C₆ alkyl radical; amonohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl) radical; a(C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical; anaryl radical; a benzyl radical; an amido(C₁-C₆ alkyl) radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl)radical, wherein the amine is protected with a radical chosen from(C₁-C₆)alkylcarbonyl, carbamyl, and (C₁-C₆)alkylsulphonyl; two of theradicals R₈, R₉ and R₁₀ may also form, together with the nitrogen atomto which they are attached, a saturated 5- or 6-membered ring containingcarbon or capable of containing at least one heteroatom such as, forexample, a pyrrolidine ring, a piperidine ring, a piperazine ring or amorpholine ring, it being possible for the ring to be unsubstituted orsubstituted with a substituent selected from a halogen atom, a hydroxylradical, a C₁-C₆ alkyl radical, a monohydroxy(C₁-C₆ alkyl) radical, apolyhydroxy(C₂-C₆ alkyl) radical, a nitro radical, a cyano radical, acyano(C₁-C₆ alkyl) radical, a C₁-C₆ alkoxy radical, atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical, an amido radical, analdehydo radical, a carboxyl radical, a keto(C₁-C₆ alkyl) radical, athio radical, a thio(C₁-C₆ alkyl) radical, a (C₁-C₆)alkylthio radical,an amino radical, an amino radical protected with a radical chosen from(C₁-C₆)alkylcarbonyl, carbamyl, and (C₁-C₆)alkylsulphonyl; one of theradicals R₈, R₉ and R₁₀ may also be chosen from the group Z′, having thesame definition as the group Z, and which is identical or different fromthe group Z;

R₁₁ is chosen from one of the two valencies of a linking arm B; a C₁-C₆alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆alkyl) radical; an aryl radical; a benzyl radical; an amino(C₁-C₆ alkyl)radical, an amino(C₁-C₆ alkyl) radical, wherein the amine is protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; a carboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆alkyl) radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; asulphonamido(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylketo(C₁-C₆alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylsulphonamido(C₁-C₆ alkyl) radical;

x and y are the integers 0 or 1; with the following conditions:

in the unsaturated cationic groups of formula (II):

when x is 0, the linking arm D is attached to the nitrogen atom;

when x is 1, the linking arm D is attached to one of the members E, G, Jor L,

y is 1:

1) when the members E, G, J and L are simultaneously a carbon atom, andR₇ is carried by the nitrogen atom of the unsaturated ring; or

2) when at least one of the members E, G, J and L is a nitrogen atomonto which the radical R₇ is attached;

in the unsaturated cationic groups of formula (III):

when x is 0, the linking arm D is attached to the nitrogen atom;

when x is 1, the linking arm D is attached to one of the members E, G,J, L or M;

y is 1 when at least one of the members E, G, J, L and M is a divalentatom, and R₇ is carried by the nitrogen atom of the unsaturated ring;

in the cationic groups of formula (IV):

if x is 0, then the linking arm D is attached to the nitrogen atomcarrying the radicals R₈ to R₁₀,

if x is 1, then two of the radicals R₈ to R₁₀ conjointly form with thenitrogen atom to which they are attached a saturated 5- or 6-memberedring as defined above; and the linking arm D is carried by a carbon atomof the said saturated ring;

X⁻ is chosen from monovalent and divalent anions; in one embodiment ofthe invention, X chosen from (i) a halogen atom such as chlorine,bromine, fluorine and iodine, (ii) a hydroxide, (iii) a hydrogensulphate, and (iv) a (C₁-C₆)alkylsulphate such as, for example, methylsulphate and ethyl sulphate;

it being understood that:

(i) the number of cationic groups Z is at least equal to 1,

(ii) the formula (I) does not designate the compounds of the formula(VI):

in which

R₁″, R₂″, R₃″ and R₄″, which are identical or different, are chosen froma hydrogen atom, a halogen atom, an alkyl radical, and a hydroxylradical,

R₅″ is chosen from a hydrogen atom and an alkyl radical,

R₈″ and R₉″, which are identical or different, are chosen from an alkylradical, a mono- or polyhydroxyalkyl radical, and an aryl radical,

D has the same meanings as in formula (I),

X⁻ designates an anion.

In the above formulae (I), (II), (III) and (IV), the alkyl and alkoxyradicals may be linear or branched.

The compounds of formula (I) may be optionally salified with stronginorganic acids such as HCl, HBr, and H₂SO₄, or organic acids such asacetic, tartaric, lactic, citric and succinic acids.

Examples of the rings of the unsaturated groups Z of formula (II),above, include the pyrrole, imidazole, pyrazole, oxazole, thiazole, andtriazole rings.

The rings of the unsaturated groups Z of formula (III), above, may be,for example, the pyridine, pyrimidine, pyrazine, oxazine and triazinerings.

In one embodiment of invention, the cationic aminodianthraquinones offormula (I) are chosen from the compounds of the formulae (I)₂ to (I)₁₂:

The cationic aminodianthraquinones of formula (I) in accordance with theinvention can be easily obtained, according to generally well knownstate of the art methods and in particular, for example, by:

condensation of two anthraquinone molecules containing a haloalkylradical with a molecule of a compound carrying two tertiary amineradicals separated by a linking arm B as defined in formula (I)described above, or alternatively,

condensation of two anthraquinone molecules containing a tertiary amineradical with a molecule of a compound carrying two halogen radicalsseparated by a linking arm B as defined in formula (I) described above,or alternatively,

(a) condensation of an anthraquinone molecule containing a tertiaryamine radical with a molecule of a compound carrying two halogenradicals separated by a linking arm B as defined in formula (I)described above, and

(b) condensation of a second anthraquinone molecule different from thefirst and also containing a tertiary amine radical, or alternatively,

(a) condensation of an anthraquinone molecule carrying a haloalkylradical with a molecule of a compound carrying two tertiary amineradicals separated by a linking arm B as defined in formula (I)described above, and

(b) condensation of a second anthraquinone molecule different from thefirst and also carrying a haloalkyl radical, or alternatively,

condensation of an anthraquinone molecule containing a tertiary amineradical with an anthraquinone molecule containing a haloalkyl radical.

The quaternization step is generally, for the sake of convenience, thelast step in the synthesis, but may occur earlier in the sequence ofreactions leading to the preparation of the compounds of formula (I).

A subject of the invention is also dyeing compositions for keratinousmaterials, comprising, in a medium appropriate for dyeing, an effectivequantity for dyeing keratinous materials of at least one cationic

aminodianthraquinone as defined above by formula (I).

Another subject of the invention is compositions for the direct dyeingof human keratinous fibers such as hair, characterized in that itcomprises, in a medium appropriate for dyeing, an effective quantity fordyeing keratinous fibers of at least one cationic aminodianthraquinoneas defined above by formula (I).

Another subject of the invention is the use of cationicaminodianthraquinones of formula (I), for which B, R₁, R₂, R₃, R₄, R₅,R′₁, R′₂, R′₃, R′₄ and R′₅ have the same meanings as previouslydescribed, it being understood that the number of cationic groups Z isat least equal to 1, as direct dyes, in, or for the preparation of,dyeing compositions for keratinous materials, for example humankeratinous fibers such as hair.

However other characteristics, aspects and advantages of the inventionwill emerge even more clearly on reading the description which follows,as well as the various concrete, but not at all limiting, examplesintended to illustrate it.

In one embodiment of the dyeing compositions in accordance with theinvention, the amount of the at least one cationicaminodianthraquinone(s) of formula (I), or an addition salt thereof, inthe dyeing composition ranges from about 0.005 to about 12%, relative tothe total weight of the dyeing composition. In another embodiment, theamount of the at least one aminodianthraquinone, or the acid additionsalt thereof, ranges from about 0.05 to about 6% by weight, relative tothe total weight of the composition.

The cationic aminodianthraquinones of formula (I) in accordance with theinvention may also serve, in the well-known oxidation dyeing methods,using oxidation dyes (oxidation dye precursors and optionally couplers),to give the colors obtained with the oxidation dyes different shades orincrease their shimmer.

In order to obtain a variety of colors, the dyeing composition accordingto the invention may also contain, in addition to the cationicaminodianthraquinones of formula (I), at least one additional direct dyethat is conventionally used in the art. Examples of the at least onadditional direct dye include:

nitrophenylenediamines, nitrodiphenylamines, nitroanilines, nitrophenolethers, nitrophenols, and nitropyridines; and

other anthraquinone dyes different from those in accordance with thepresent invention; and

mono- or diazo, triarylmethane, azine, acridine and xanthene dyes; and

metal-containing dyes.

The total amount of all these other direct addition dyes in thecomposition according to the present invention may range from about 0.5to about 10% by weight, relative to the total weight of the dyeingcomposition.

The medium (or carrier) appropriate for dyeing is generally water or amixture of water and at least one organic solvent for solubilizing thecompounds which would not be sufficiently soluble in water. Examples oforganic solvents include lower C₁-C₄ alkanols, such as ethanol andisopropanol; glycerol; glycols and glycol ethers, such as2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether; aswell as aromatic alcohols, such as benzyl alcohol or phenoxyethanol; andsimilar products and mixtures thereof.

In one embodiment of the invention, the solvents may be present in anamount ranging from approximately 1 to approximately 40% by weight,relative to the total weight of the dyeing composition. In anotherembodiment of the invention, the amount of solvents may range fromapproximately 5 to approximately 30% by weight, relative to the totalweight of the dyeing composition. It is also possible to add to thecomposition according to the invention fatty amides such as mono- anddiethanolamides of acids derived from copra, lauric acid and oleic acid,in amounts ranging from about 0.05 to about 10% by weight, relative tothe total weight of the composition.

It is also possible to add to the composition according to the inventionwell-known state of the art surfactants of the anionic, cationic,nonionic, amphoteric or zwitterionic type, or mixtures thereof. In oneembodiment of the invention, the surfactants can be present in an amountranging from about 0.1 to about 50% by weight, relative to the totalweight of the composition. In another embodiment of the invention, thesurfactants can be present in an amount ranging from about 1 to about20% by weight, relative to the total weight of the composition.

It is also possible to use thickening agents in a proportion rangingfrom about 0.2 to about 5%.

The dyeing composition according to the invention may contain, inaddition, various customary adjuvants such as antioxidants, perfumes,sequestering agents, dispersing agents, hair conditioners,preservatives, and opacifying agents, as well as any other adjuvantnormally used in dyeing keratinous materials.

Of course, persons skilled in the art will be careful to choose theoptional additional compound(s) mentioned above such that theadvantageous properties intrinsically attached to the dyeing compositionaccording to the invention are not, or not substantially, adverselymodified by the addition(s) envisaged.

The pH of the dyeing composition in accordance with the invention mayvary between approximately 3 and approximately 12. In one embodiment ofthe invention, the pH varies between approximately 5 and approximately11. The pH can be adjusted to the desired value by means of acidifyingor alkalinizing agents normally used in dyeing keratinous fibres.

Among the acidifying agents, there may be mentioned, by way of example,inorganic or organic acids such as hydrochloric acid, orthophosphoricacid, sulphuric acid, carboxylic acids such as acetic acid, tartaricacid, citric acid, lactic acid, and sulphonic acids.

Suitable alkalinizing agents include ammonium hydroxide, alkali metalcarbonates, alkanolamines such as mono-, di- and triethanolamines, aswell as their derivatives, sodium and potassium hydroxides, and thecompounds of the formula (V):

in which W is a propylene residue which is unsubstituted or substitutedwith a group chosen from a hydroxyl group and a C₁-C₆ alkyl radical;R₁₂, R₁₃, R₁₄ and R₁₅, which are identical or different, are chosen froma hydrogen atom, a C₁-C₆ alkyl radical, and a hydroxy(C₁-C₆ alkyl)radical.

The dyeing composition according to the invention may be provided invarious forms, such as in the form of liquids, creams, gels or in anyother form appropriate for dyeing keratinous fibers, and moreparticularly human keratinous fibers and in particular hair. Inparticular, it can be packaged under pressure in an aerosol can in thepresence of a propellant and can form a foam.

Another subject of the present invention relates to a method for dyeingkeratinous fibers, in particular human keratinous fibers such as hair,by direct dyeing, comprising allowing a dyeing composition containing atleast one cationic aminodianthraquinone of formula (I) to act on dry orwet keratinous fibers. It is possible to use the composition accordingto the invention as a leave-in composition, that is to say that afterapplying the composition to the fibers, they are dried withoutintermediate rinsing.

In one embodiment, the process comprises allowing the composition to acton the fibers for an exposure time ranging from approximately 3 toapproximately 60 minutes, rinsing the fibers, optionally washing thefibers, and rinsing the fibers again and drying the fibers. In anotherembodiment of the invention, the process is similar to that justdescribed, except that the exposure time ranges from approximately 5 toapproximately 45 minutes.

Concrete and nonlimiting examples illustrating the invention will now begiven.

EXAMPLES OF PREPARATION Example 1

Synthesis of the Compound of Formula (I)₁

7.0 g (0.0207 mol) of1-(3-dimethylaminopropylamino)-4-methylaminoanthraquinone(RN-25264-26-0) and 2.09 g (0.1305 mol) of 1,3-dibromopropane(RN-109-64-8) were suspended in 50 ml of 2-methyl-1-propanol. Themixture was then heated, with stirring, at the reflux temperature of the2-methyl-1-propanol for 4 hours (which corresponds to the disappearanceof the starting anthraquinone in thin-layer chromatography); and thenthe boiling product was dewatered, it was washed with2-methyl-1-propanol and it was made into a paste again in absoluteethanol.

After drying at 50° C. under vacuum in the presence of phosphoricanhydride, 7.7 g of deep blue crystals were obtained which melt at214-216° C. (Kofler) and whose elemental analysis calculated forC₄₃H₅₂N₆O₄Br₂+2H₂O was:

% C H N O Br theory 56.58 6.18 9.21 10.52 17.51 found 56.89 6.33 9.0110.59 17.52

Example 2

Synthesis of the Compound of Formula (I)₂

33.0 g (0.1 mol) of 1-(2-bromoethylamino)anthraquinone (RN 3591-05-7)and 10.2 g (0.05 mol) of 1,4-diimidazol-1-ylbutane (RN 69506-86-1) in180 ml of isobutanol (disappearance of the starting anthraquinone inthin-layer chromatography) were heated under reflux for 7 hours.

The suspension obtained was cooled to room temperature, diluted with 180ml of absolute ethanol and dewatered.

After purification by recrystallization from 90% ethanol under reflux,drying at 50° C. under vacuum in the presence of phosphoric anhydride,32.8 g of red crystals melting at 224-225° C. (Kofler) were obtainedwhose elemental analysis calculated for C₄₂H₃₈N₆O₄Br₂+H₂O was:

% C H N O Br theory 58.08 4.64 9.68 9.21 18.40 found 58.28 4.68 9.459.10 18.46

EXAMPLES OF DYEING COMPOSITIONS Examples 3 and 4

The two dyeing compositions combined in the following table wereprepared:

(all contents expressed in grams—A.M. designates active material)

Example 3 Example 4 Dye of formula (I)₁ 0.456 Dye of formula (I)₂ 0.434Hydroxyethylcellulose sold under the name 0.72 0.72 NATROSOL 250 MR bythe company Aqualon Benzyl alcohol 4 4 Polyethylene glycol containing 6ethylene oxide 6 6 units (C8-C10)Alkylpolyglucoside in aqueous solution4.5 A.M. 3 A.M. containing 60% A.M. sold under the name ORAMIX CG 110 bythe company Seppic Phosphate buffer pH 7 qs 100 Phosphate buffer pH 9(boric acid/potassium 100 chloride/sodium hydroxide qs

Each of the above compositions was applied to locks of permanently-wavedor natural grey hair, which was 90% white, and allowed to act for 20minutes. After rinsing with running water and drying, the hair was dyedwith a shade which is expressed in the table below.

Composition of Example 3 Deep blue Composition of Example 4Iridescent-copper coloured

What is claimed is:
 1. A direct dyeing composition for human keratinousfibers comprising, in a medium appropriate for dyeing, a quantity of atleast one cationic aminodianthraquinone of formula (I), or an acidaddition salt thereof, effective for dyeing said human keratinousfibers:

in which: B is a linking arm chosen from a linear alkyl chain and abranched alkyl chain, which may be interrupted by one or more groups Z,defined below, one or more heteroatoms, or a mixture of one or moregroups Z and one or more heteroatoms, which may be unsubstituted orsubstituted with at least one hydroxyl or C₁-C₆ alkoxy radical, andwhich may carry at least one ketone function; R₁, R₂, R₃, R₄, R′₁, R′₂,R′₃ and R′₄, which may be identical or different, are chosen from one ofthe two valencies of a linking arm B; a hydrogen atom; a halogen atom; agroup Z, defined below; a (C₁-C₆)alkyl radical; a monohydroxy(C₁-C₆alkyl) radical; a polyhydroxy(C₂-C₆ alkyl) radical; a cyano radical; anitro radical; a carboxyl radical; a carbamyl radical; a sulpho radical;an unsubstituted amino radical; a substituted amino radical NHR′₅,wherein R′₅ has the same definition as R₅ defined below, and wherein R′₅may be identical to or different from R₅ below; and OR₆, SR₆, OR′₆, andSR′₆, wherein R₆ and R′₆ are as defined below; R₅ and R′₅, which may beidentical or different, are chosen from one of the two valencies of alinking arm B; a hydrogen atom; a group Z, defined below; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; a benzylradical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical;an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a thiocarbamyl(C₁-C₆alkyl) radical; a trifluoro(C₁-C₆ alkyl) radical; a sulpho(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆alkyl) radical; an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarbonyl(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl) radicalwherein the alkyl is unsubstituted or substituted with at least onehydroxyl radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical, andwherein the amine is substituted with one or two radicals, identical ordifferent, chosen from the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl),polyhydroxy(C₂-C₆ alkyl), (C₁-C₆)alkylcarbonyl, carbamyl,N-(C₁-C₆)alkylcarbamyl, N,N-di(C₁-C₆)alkylcarbamyl,(C₁-C₆)alkylsulphonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl and thiocarbamyl radicals, or from the group Z,defined below, or which may form, together with the nitrogen atom towhich they are attached, a 5- or 6-membered ring containing carbon orcontaining at least one heteroatom R₆ and R′₆, which may be identical ordifferent, are chosen from one of the two valencies of a linking arm B;a hydrogen atom; a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl)radical; a polyhydroxy(C₂-C₆ alkyl) radical; a group Z, defined below; a(C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; a benzyl radical; acarboxy(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl)radical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical;an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆alkyl) radical; an aminosulphonyl(C₁-C₆ alkyl) radical; anN-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; an N,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarbonyl(C₁-C₆alkyl) radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical; anamino(C₁-C₆ alkyl) radical, wherein the alkyl is unsubstituted orsubstituted with at least one hydroxyl radical, and wherein the amine issubstituted with one or two radicals, identical or different, chosenfrom the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl), polyhydroxy(C₂-C₆alkyl), (C₁-C₆)alkylcarbonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, carbamyl, N-(C₁-C₆)alkylcarbamyl,N,N-di(C₁-C₆)alkylcarbamyl, thiocarbamyl and (C₁-C₆)alkylsulphonylradicals, or from the groups Z, defined below, or which may form,together with the nitrogen atom to which they are attached, a 5- or6-membered ring containing carbon or containing at least one heteroatom;Z is chosen from the unsaturated cationic groups of the formulae (II)and (III), and the saturated cationic groups of the formula (IV)

in which D is a linking arm chosen from a linear and branched alkylchain, which may be interrupted by one or more heteroatoms, which may beunsubstituted or substituted with at least one radical chosen fromhydroxyl and C₁-C₆ alkoxy, and which may carry at least one ketonefunction; the members E, G, J, L and M, which are identical ordifferent, are chosen from carbon, oxygen, sulphur or nitrogen atoms; nis an integer ranging from 0 to 4; m is an integer ranging from 0 to 5;the radicals R, which are identical or different, are chosen from one ofthe two valencies of a linking arm B; a group Z′, wherein Z′ has thesame definition as Z, and wherein the group Z′ is identical or differentfrom the group Z; a halogen atom; a hydroxyl radical; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a nitro radical; a cyano radical; a cyano(C₁-C₆ alkyl) radical;a C₁-C₆ alkoxy radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; anamido radical; an aldehydo radical; a carboxyl radical; a C₁-C₆alkylcarbonyl radical; a thio radical; a thio(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylthio radical; an amino radical; an amino radical protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl and(C₁-C₆)alkylsulphonyl; and an NHR″ or NR″R′″ group, wherein R″ and R″,which are identical or different, are chosen from a C₁-C₆ alkyl radical,a monohydroxy(C₁-C₆ alkyl) radical, and a polyhydroxy(C₂-C₆ alkyl)radical; R₇ is chosen from one of the two valencies of a linking arm B;a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl)radical; a carbamyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆alkyl) radical; a benzyl radical; a group Z′, wherein Z′ has the samedefinition as Z, and wherein the group Z′ is identical or different fromthe group Z; R₈, R₉ and R₁₀, which are identical or different, arechosen from one of the two valencies of a linking arm B; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl)radical; an aryl radical; a benzyl radical; an amido(C₁-C₆ alkyl)radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; and anamino(C₁-C₆ alkyl) radical, wherein the amine is protected with aradical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; two of the radicals R₈, R₉ and R₁₀ may also form,together with the nitrogen atom to which they are attached, a saturated5- or 6-membered ring containing atoms selected from carbon andheteroatoms, it being possible for the said ring to be unsubstituted orsubstituted with a halogen atom, a hydroxyl radical, a C₁-C₆ alkylradical, a monohydroxy(C₁-C₆ alkyl) radical, a polyhydroxy(C₂-C₆ alkyl)radical, a nitro radical, a cyano radical, a cyano(C₁-C₆ alkyl) radical,a C₁-C₆ alkoxy radical, a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical, anamido radical, an aldehydo radical, a carboxyl radical, a keto(C₁-C₆alkyl) radical, a thio radical, a thio(C₁-C₆ alkyl) radical, a(C₁-C₆)alkylthio radical, an amino radical, an amino radical protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl and(C₁-C₆)alkylsulphonyl; one of the radicals R₈, R₉ and R₁₀ may alsorepresent a group Z′, wherein Z′ has the same definition as Z, andwherein the group Z′ is identical or different from the group Z;provided that in formula (IV), two of the radicals R₈, R₉ and R₁₀ form aring chosen from pyrrolidine, piperidine, piperazine, and morpholine,said ring is unsubstituted or substituted with a halogen atom, ahydroxyl radical, a C₁-C₆ alkyl radical, a monohydroxy(C₁-C₆ alkyl)radical, a polyhydroxy(C₂-C₆ alkyl) radical, a nitro radical, a cyanoradical, a cyano(C₁-C₆ alkyl) radical, a C₁-C₆ alkoxy radical, atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical, an amido radical, analdehydo radical, a carboxyl radical, a (C₁-C₆ alkyl)carbonyl radical, athio radical, a thio(C₁-C₆ alkyl) radical, a (C₁-C₆)alkylthio radical,an amino radical, and an amino radical protected with a radical chosenfrom (C₁-C₆)alkylcarbonyl, carbamyl and (C₁-C₆)alkylsulphonyl; R₁₁ ischosen from one of the two valencies of a linking arm B; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; an aryl radical; a benzyl radical; an amino(C₁-C₆ alkyl)radical; an amino(C₁-C₆ alkyl) radical, wherein the amine is protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; a carboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆alkyl) radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; asulphonamido(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylketo(C₁-C₆alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylsulphonamido(C₁-C₆ alkyl) radical; x and y are integersequal to 0 or 1; with the following conditions: in the unsaturatedcationic groups of formula (II): when x is 0, the linking arm D isattached to the nitrogen atom, when x is 1, the linking arm D isattached to one of E, G, J or L, y may only be 1: 1) when the E, G, Jand L are simultaneously a carbon atom, and the radical R₇ is carried bythe nitrogen atom of the unsaturated ring; or 2) when at least one of E,G, J and L represents a nitrogen atom onto which the radical R₇ isattached; in the unsaturated cationic groups of formula (III): when x is0, the linking arm D is attached to the nitrogen atom; when x is 1,thelinking arm D is attached to one of E, G, J, L or M, y may only take thevalue 1 when at least one of E, G, J, L and M is a divalent atom, andthe radical R7 is carried by the nitrogen atom of the unsaturated ring;in the cationic groups of formula (IV): when x is 0, then the linkingarm D is attached to the nitrogen atom carrying the radicals R8 to R10,when x is 1, then two of the radicals R₈ to R₁₀ conjointly form, withthe nitrogen atom to which they are attached, a saturated 5- or6-membered ring as defined above and the linking arm D is carried by acarbon atom of the saturated ring; and X is chosen from monovalent anddivalent anions; it being understood that: (i) the number of cat ionicgroups Z is at least equal to 1, (ii) the formula (I) does not designatethe compounds of the formula (VI):

in which R₁″, R₂″, R₃″ and R₄″, which are identical or different, arechosen from a hydrogen atom, a halogen atom, an alkyl radical and ahydroxyl radical; R₅″ is chosen from a hydrogen atom, an alkyl radical,and a monohydroxy(C₁-C₆ alkyl) radical; R₈″ and R₉″, which are identicalor different, are chosen from an alkyl, a mono- or polyhydroxyalkylradical, and an aryl radical, D has the same meanings as in formula (I),X⁻ is an anion.
 2. A composition according to claim 1, wherein saidcomposition has a pH ranging from about 3 to about
 12. 3. A compositionaccording to claim 1, wherein said at least one cationicaminodianthraquinone of formula (I) is present in said composition in anamount ranging from about 0.005 to about 12% by weight relative to thetotal weight of the composition.
 4. A composition according to claim 3,wherein the said at least one cationic aminodianthraquinone of formula(I) is present in an amount ranging from about 0.05 to about 6% byweight relative to the total weight of the composition.
 5. A compositionaccording to claim 1, wherein said composition further comprises atleast one additional direct dye chosen from nitrobenzene dyes,anthraquinone dyes different from those of formula (I), mono- and diazodyes, triarylmethane dyes, azine dyes, acridine dyes, xanthene dyes, andmetal-containing dyes.
 6. A composition according to claim 1, whereinthe medium appropriate for dyeing is an aqueous medium chosen from waterand a mixture of water and organic solvents chosen from alcohols,glycols and glycol ethers, wherein said medium is present in saidcomposition in an amount ranging from about 1% to about 40% by weightrelative to the total weight of the composition.
 7. A compositionaccording to claim 6, wherein said medium is present in an amountranging from about 5% to about 30% by weight relative to the totalweight of the composition.
 8. A method of direct dyeing keratinousfibers, said method comprising: applying a direct dyeing composition tosaid fibers, wherein said fibers can be dry or wet, and wherein saiddirect dyeing composition comprises, in a medium appropriate for dyeing,a quantity of at least one cationic aminodianthraquinone of formula (I),or an acid addition salt thereof, effective for dyeing said keratinousfibers:

in which: B is a linking arm chosen from a linear alkyl chain and abranched alkyl chain, which may be interrupted by one or more groups Z,defined below, one or more heteroatoms, or a mixture of one or moregroups Z and one or more heteroatoms, which may be unsubstituted orsubstituted with at least one hydroxyl or C₁-C₆ alkoxy radical, andwhich may carry at least one ketone function; R₁, R₂, R₃, R₄, R′₁, R′₂,R′₃ and R′₄, which may be identical or different, are chosen from one ofthe two valencies of a linking arm B; a hydrogen atom; a halogen am; agroup Z, defined below; a (C₁-C₆)alkyl radical; a monohydroxy(C₁-C₆alkyl) radical; a polyhydroxy(C₂-C₆ alkyl) radical; a cyano radical; anitro radical; a carboxyl radical; a carbamyl radical; a sulpho radical;an unsubstituted amino radical; a substituted amino radical NHR′₅,wherein R′₅ has the same definition as R₅ defined below, and wherein R′₅may be identical to or different from R₅ below; and OR₆, SR₆, OR′₆ , andSR′₆, wherein R₆ and R′₆ are as defined below; R₅ and R′₅, which may beidentical or different, are chosen from one of the two valencies of alinking arm B; a hydrogen atom; a group Z defined below; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; a benzylradical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical;an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a thiocarbamyl(C₁-C₆alkyl) radical; a trifluoro(C₁-C₆ alkyl) radical; a sulpho(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆alkyl) radical; an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarbonyl(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl) radicalwherein the alkyl is unsubstituted or substituted with at least onehydroxyl radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical, andwherein the amine is substituted with one or two radicals, identical ordifferent, chosen from the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl),polyhydroxy(C₂-C₆ alkyl), (C₁-C₆)alkylcarbonyl, carbamyl,N-(C₁-C₆)alkylcarbamyl, N,N-di(C₁-C₆)alkylcarbamyl,(C₁-C₆)alkylsulphonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl and thiocarbamyl radicals, or from the group Z,defined below, or which may form, together with the nitrogen atom towhich they are attached, a 5- or 6-membered ring containing carbon orcontaining at least one heteroatom; R₆ and R′₆, which may be identicalor different, are chosen from one of the two valencies of a linking armB; a hydrogen atom; a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl)radical; a polyhydroxy(C₂-C₆ alkyl) radical; a group Z, defined below; a(C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; a benzyl radical; acarboxy(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl)radical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical;an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆alkyl) radical; an aminosulphonyl(C₁-C₆ alkyl) radical; anN-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆₎alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarbonyl(C₁-C₆alkyl) radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical; anamino(C₁-C₆ alkyl) radical, wherein the alkyl is unsubstituted orsubstituted with at least one hydroxyl radical, and wherein the amine issubstituted with one or two radicals, identical or different, chosenfrom the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl), polyhydroxy(C₂-C₆alkyl), (C₁-C₆)alkylcarbonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, carbamyl, N-(C₁-C₆)alkylcarbamyl, N,N-di(C₁-C₆)alkylcarbamyl, thiocarbamyl and (C₁-C₆)alkylsulphonylradicals, or from the groups Z, defined below, or which may form,together with the nitrogen atom to which they are attached, a 5- or6-membered ring containing carbon or containing at least one heteroatom;Z is chosen from the unsaturated cationic groups of the formulae (II)and (III), and the saturated cationic groups of the formula (IV)

in which D is a linking arm chosen from a linear and branched alkylchain, which may be interrupted by one or more heteroatoms, which may beunsubstituted or substituted with at least one radical chosen fromhydroxyl and C₁-C₆ alkoxy, and which may carry at least one ketonefunction; the members E, G, J, L and M, which are identical ordifferent, are chosen from carbon, oxygen, sulphur or nitrogen atoms; nis an integer ranging from 0 to 4; m is an integer ranging from 0 to 5;the radicals R, which are identical or different, are chosen from one ofthe two valencies of a linking arm B; a group Z′, wherein Z′ has thesame definition as Z, and wherein the group Z′ is identical or differentfrom the group Z; a halogen atom; a hydroxyl radical; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a nitro radical; a cyano radical; a cyano(C₁-C₆ alkyl) radical;a C₁-C₆ alkoxy radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; anamido radical; an aldehydo radical; a carboxyl radical; a C₁-C₆alkylcarbonyl radical; a thio radical; a thio(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylthio radical; an amino radical; an amino radical protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl and(C₁-C₆)alkylsulphonyl; and an NHR″ or NR″R′″ group, wherein R″ and R′″,which are identical or different, are chosen from a C₁-C₆ alkyl radical,a monohydroxy(C₁-C₆ alkyl) radical, and a polyhydroxy(C₂-C₆ alkyl)radical; R₇ is chosen from one of the two valencies of a linking arm B;a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl)radical; a carbamyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆alkyl) radical; a benzyl radical; a group Z′, wherein Z′ has the samedefinition as Z, and wherein the group Z′ is identical or different fromthe group Z; R₈, R₉ and R₁₀, which are identical or different, arechosen from one of the two valencies of a linking arm B; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl)radical; an aryl radical; a benzyl radical; an amido(C₁-C₆ alkyl)radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; and anamino(C₁-C₆ alkyl) radical, wherein the amine is protected with aradical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; two of the radicals R₈, R₉ and R₁₀ may also form,together with the nitrogen atom to which they are attached, a saturated5- or 6-membered ring containing atoms selected from carbon andheteroatoms, it being possible for the said ring to be unsubstituted orsubstituted with a halogen atom, a hydroxyl radical, a C₁-C₆ alkylradical, a monohydroxy(C₁-C₆ alkyl) radical, a polyhydroxy(C₂-C₆ alkyl)radical, a nitro radical, a cyano radical, a cyano(C₁-C₆ alkyl) radical,a C₁-C₆ alkoxy radical, a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical, anamido radical, an aldehydo radical, a carboxyl radical, a keto(C₁-C₆alkyl) radical, a thio radical, a thio(C₁-C₆ alkyl) radical, a(C₁-C₆)alkylthio radical, an amino radical, an amino radical protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl and(C₁-C₆)alkylsulphonyl; one of the radicals R₈, R₉ and R₁₀ may alsorepresent a group Z′, wherein Z′ has the same definition as Z, andwherein the group Z′ is identical or different from the group Z; R₁₁ ischosen from one of the two valencies of a linking arm B; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; an aryl radical; a benzyl radical; an amino(C₁-C₆ alkyl)radical; an amino(C₁-C₆ alkyl) radical, wherein the amine is protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; a carboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆alkyl) radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; asulphonamido(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylketo(C₁-C₆alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylsulphonamido(C₁-C₆ alkyl) radical; x and y are integersequal to 0 or 1; with the following conditions: in the unsaturatedcationic groups of formula (II): when x is 0, the linking arm D isattached to the nitrogen atom, when x is 1, the linking arm D isattached to one of E, G, J or L, y may only be 1: 1) when the E, G, Jand L are simultaneously a carbon atom, and the radical R₇ is carried bythe nitrogen atom of the unsaturated ring; or 2) when at least one of E,G, J and L represents a nitrogen atom onto which the radical R₇ isattached; in the unsaturated cationic groups of formula (III): when x is0, the linking arm D is attached to the nitrogen atom; when x is 1, thelinking arm D is attached to one of E, G, J, L or M, y may only take thevalue 1 when at least one of E, G, J, L and M is a divalent atom, andthe radical R₇ is carried by the nitrogen atom of the unsaturated ring;in the cationic groups of formula (IV): when x is 0, then the linkingarm D is attached to the nitrogen atom carrying the radicals R₈ to R₁₀,when x is 1, then two of the radicals R₈ to R₁₀ conjointly form, withthe nitrogen atom to which they are attached, a saturated 5- or6-membered ring as defined above and the linking arm D is carried by acarbon atom of the saturated ring; X is chosen from monovalent anddivalent anions; it being understood that: (i) the number of cationicgroups Z is at least equal to I, (ii) the formula (I) does not designatethe compounds of the formula (VI):

in which R₁″, R₂″, R₃″ and R₄″, which are identical or different, arechosen from a hydrogen atom, a halogen atom, an alkyl radical and ahydroxyl radical; R₅″ is chosen from a hydrogen atom, an alkyl radical,and a monohydroxy(C₁-C₆ alkyl) radical; R₈″ and R₉″, which are identicalor different, are chosen from an alkyl, a mono- or polyhydroxyalkylradical, and an aryl radical, D has the same meanings as in formula (I),X⁻ is an anion; and drying said fibers without an intermediate rinsingstep.
 9. A method of direct dyeing keratinous fibers, said methodcomprising: applying a direct dyeing composition to said fibers, whereinsaid fibers can be wet or dry, and wherein said direct dyeingcomposition comprises, in a medium appropriate for dyeing, a quantity ofat least one cationic aminodianthraquinone of formula (I), or an acidaddition salt thereof, effective for dyeing said keratinous fibers:

in which: B is a linking arm chosen from a linear alkyl chain and abranched alkyl chain, which may be interrupted by one or more groups Z,defined below, one or more heteroatoms, or a mixture of one or moregroups Z and one or more heteroatoms, which may be unsubstituted orsubstituted with at least one hydroxyl or C₁-C₆ alkoxy radical, andwhich may carry at least one ketone function; R₁, R₂, R₃, R₄, R′₁, R′₂,R′₃ and R′₄, which may be identical or different, are chosen from one ofthe two valencies of a linking arm B; a hydrogen atom; a halogen atom; agroup Z, defined below; a (C₁-C₆)alkyl radical; a monohydroxy(C₁-C₆alkyl) radical; a polyhydroxy(C₂-C₆ alkyl) radical; a cyano radical; anitro radical; a carboxyl radical; a carbamyl radical; a sulpho radical;an unsubstituted amino radical; a substituted amino radical NHR′₅,wherein R′₅ has the same definition as R₅ defined below, and wherein R′₅may be identical to or different from R₅ below; and OR₆, SR₆, OR′₆, andSR′₆, wherein R₆ and R′₆ are as defined below; R₅ and R′₅, which may beidentical or different, are chosen from one of the two valencies of alinking arm B; a hydrogen atom; a group Z, defined below; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; a benzylradical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical;an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a thiocarbamyl(C₁-C₆alkyl) radical; a trifluoro(C₁-C₆ alkyl) radical; a sulpho(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; an aminosulphonyl(C₁-C₆alkyl) radical; an N-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylcarbonyl(C₁-C₆ alkyl) radical; an amino(C₁-C₆ alkyl) radicalwherein the alkyl is unsubstituted or substituted with at least onehydroxyl radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical, andwherein the amine is substituted with one or two radicals, identical ordifferent, chosen from the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl),polyhydroxy(C₂-C₆ alkyl), (C₁-C₆)alkylcarbonyl, carbamyl,N-(C₁-C₆)alkylcarbamyl, N,N-di(C₁-C₆)alkylcarbamyl,(C₁-C₆)alkylsulphonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl and thiocarbamyl radicals, or from the group Z,defined below, or which may form, together with the nitrogen atom towhich they are attached, a 5- or 6-membered ring containing carbon orcontaining at least one heteroatom; R₆ and R′₆, which may be identicalor different, are chosen from one of the two valencies of a linking armB; a hydrogen atom; a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl)radical; a polyhydroxy(C₂-C₆ alkyl) radical; a group Z, defined below; a(C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; an aryl radical; a benzyl radical; acarboxy(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl)radical; a cyano(C₁-C₆ alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical;an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆alkyl) radical; an aminosulphonyl(C₁-C₆ alkyl) radical; anN-Z-aminosulphonyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; anN,N-di(C₁-C₆)alkylaminosulphonyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarbonyl(C₁-C₆alkyl) radical; an amino(C₁-C₆ alkyl) radical, wherein the alkyl isunsubstituted or substituted with at least one hydroxyl radical; anamino(C₁-C₆ alkyl) radical, wherein the alkyl is unsubstituted orsubstituted with at least one hydroxyl radical, and wherein the amine issubstituted with one or two radicals, identical or different, chosenfrom the C₁-C₆ alkyl, monohydroxy(C₁-C₆ alkyl), polyhydroxy(C₂-C₆alkyl), (C₁-C₆)alkylcarbonyl, formyl, trifluoro(C₁-C₆)alkylcarbonyl,(C₁-C₆)alkylcarboxyl, carbamyl, N-(C₁-C₆)alkylcarbamyl, N,N-di(C₁-C₆)alkylcarbamyl, thiocarbamyl and (C₁-C₆)alkylsulphonylradicals, or from the groups Z, defined below, or which may form,together with the nitrogen atom to which they are attached, a 5- or6-membered ring containing carbon or containing at least one heteroatom;Z is chosen from the unsaturated cationic groups of the formulae (II)and (III), and the saturated cationic groups of the formula (IV)

in which D is a linking arm chosen from a linear and branched alkylchain, which may be interrupted by one or more heteroatoms, which may beunsubstituted or substituted with at least one radical chosen fromhydroxyl and C₁-C₆ alkoxy, and which may carry at least one ketonefunction; the members E, G, J, L and M, which are identical ordifferent, are chosen from carbon, oxygen, sulphur or nitrogen atoms; nis an integer ranging from 0 to 4; m is an integer ranging from 0 to 5;the radicals R, which are identical or different, are chosen from one ofthe two valencies of a linking arm B; a group Z′, wherein Z′ has thesame definition as Z, and wherein the group Z′ is identical or differentfrom the group Z; a halogen atom; a hydroxyl radical; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a nitro radical; a cyano radical; a cyano(C₁-C₆ alkyl) radical;a C₁-C₆ alkoxy radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; anamido radical; an aldehydo radical; a carboxyl radical; a C₁-C₆alkylcarbonyl radical; a thio radical; a thio(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylthio radical; an amino radical; an amino radical protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl and(C₁-C₆)alkylsulphonyl; and an NHR″ or NR″R′″ group, wherein R″ and R′″,which are identical or different, are chosen from a C₁-C₆ alkyl radical,a monohydroxy(C₁-C₆ alkyl) radical, and a polyhydroxy(C₂-C₆ alkyl)radical; R₇ is chosen from one of the two valencies of a linking arm B;a C₁-C₆ alkyl radical; a monohydroxy(C₁-C₆ alkyl) radical; apolyhydroxy(C₂-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl) radical; atri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl)radical; a carbamyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆alkyl) radical; a benzyl radical; a group Z′, wherein Z′ has the samedefinition as Z, and wherein the group Z∝ is identical or different fromthe group Z; R₈, R₉ and R₁₀, which are identical or different, arechosen from one of the two valencies of a linking arm B; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; a (C₁-C₆)alkoxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆ alkyl)radical; an aryl radical; a benzyl radical; an amido(C₁-C₆ alkyl)radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; and anamino(C₁-C₆ alkyl) radical, wherein the amine is protected with aradical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; two of the radicals R₈, R₉ and R₁₀ may also form,together with the nitrogen atom to which they are attached, a saturated5- or 6-membered ring containing atoms selected from carbon andheteroatoms, it being possible for the said ring to be unsubstituted orsubstituted with a halogen atom, a hydroxyl radical, a C₁-C₆ alkylradical, a monohydroxy(C₁-C₆ alkyl) radical, a polyhydroxy(C₂-C₆ alkyl)radical, a nitro radical, a cyano radical, a cyano(C₁-C₆ alkyl) radical,a C₁-C₆ alkoxy radical, a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical, anamido radical, an aldehydo radical, a carboxyl radical, a keto(C₁-C₆alkyl) radical, a thio radical, a thio(C₁-C₆ alkyl) radical, a(C₁-C₆)alkylthio radical, an amino radical, an amino radical protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl and(C₁-C₆)alkylsulphonyl; one of the radicals R₈, R₉ and R₁₀ may alsorepresent a group Z′, wherein Z′ has the same definition as Z, andwherein the group Z′ is identical or different from the group Z; R₁₁ ischosen from one of the two valencies of a linking arm B; a C₁-C₆ alkylradical; a monohydroxy(C₁-C₆ alkyl) radical; a polyhydroxy(C₂-C₆ alkyl)radical; an aryl radical; a benzyl radical; an amino(C₁-C₆ alkyl)radical; an amino(C₁-C₆ alkyl) radical, wherein the amine is protectedwith a radical chosen from (C₁-C₆)alkylcarbonyl, carbamyl, and(C₁-C₆)alkylsulphonyl; a carboxy(C₁-C₆ alkyl) radical; a cyano(C₁-C₆alkyl) radical; a carbamyl(C₁-C₆ alkyl) radical; a trifluoro(C₁-C₆alkyl) radical; a tri(C₁-C₆)alkylsilane(C₁-C₆ alkyl) radical; asulphonamido(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylcarboxy(C₁-C₆ alkyl)radical; a (C₁-C₆)alkylsulphinyl(C₁-C₆ alkyl) radical; a(C₁-C₆)alkylsulphonyl(C₁-C₆ alkyl) radical; a (C₁-C₆)alkylketo(C₁-C₆alkyl) radical; an N-(C₁-C₆)alkylcarbamyl(C₁-C₆ alkyl) radical; anN-(C₁-C₆)alkylsulphonamido(C₁-C₆ alkyl) radical; x and y are integersequal to 0 or 1; with the following conditions: in the unsaturatedcationic groups of formula (II): when x is 0, the linking arm D isattached to the nitrogen atom, when x is 1, the linking arm D isattached to one of E, G, J or L, y may only be 1: 1) when the E, G, Jand L are simultaneously a carbon atom, and the radical R₇ is carried bythe nitrogen atom of the unsaturated ring; or 2) when at least one of F,G, J and L represents a nitrogen atom onto which the radical R₇ isattached; in the unsaturated cationic groups of formula (III): when x is0, the linking arm D is attached to the nitrogen atom; when x is 1, thelinking arm D is attached to one of E, G, J, L or M, y may only take thevalue I when at least one of E, G, J, L and M is a divalent atom, andthe radical R₇ is carried by the nitrogen atom of the unsaturated ring;in the cationic groups of formula (IV): when x is 0, then the linkingarm D is attached to the nitrogen atom carrying the radicals R₈ to R₁₀,when x is 1, then two of the radicals R₈ to R₁₀ conjointly form, withthe nitrogen atom to which they are attached, a saturated 5- or6-membered ring as defined above and the linking arm D is carried by acarbon atom of the saturated ring; X is chosen from monovalent anddivalent anions; it being understood that: (i) the number of cationicgroups Z is at least equal to 1, (ii) the formula (I) does not designatethe compounds of the formula (VI):

in which R₁″, R₂″, R₃″ and R₄″, which are identical or different, arechosen from a hydrogen atom, a halogen atom, an alkyl radical and ahydroxyl radical; R₅″ is chosen from a hydrogen atom, an alkyl radical,and a monohydroxy(C₁-C₆ alkyl) radical; R₈″ and R₉″, which are identicalor different, are chosen from an alkyl, a mono- or polyhydroxyalkylradical, and an aryl radical, D has the same meanings as in formula (I),X is an anion; allowing said direct dyeing composition to remain incontact with said fibers for a time period ranging from approximately 3to approximately 60 minutes; rinsing said fibers; and drying saidfibers.
 10. A method according to claim 9, further comprising, aftersaid rinsing step, a washing step, and an additional rinsing step.